[go: up one dir, main page]

WO2024167347A1 - Électrode étirable, diode électroluminescente organique étirable la comprenant, et son procédé de fabrication - Google Patents

Électrode étirable, diode électroluminescente organique étirable la comprenant, et son procédé de fabrication Download PDF

Info

Publication number
WO2024167347A1
WO2024167347A1 PCT/KR2024/001917 KR2024001917W WO2024167347A1 WO 2024167347 A1 WO2024167347 A1 WO 2024167347A1 KR 2024001917 W KR2024001917 W KR 2024001917W WO 2024167347 A1 WO2024167347 A1 WO 2024167347A1
Authority
WO
WIPO (PCT)
Prior art keywords
stretchable
layer
electrode
mxene
organic light
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/KR2024/001917
Other languages
English (en)
Korean (ko)
Inventor
이태우
주환우
한신정
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
SNU R&DB Foundation
Original Assignee
Seoul National University R&DB Foundation
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Seoul National University R&DB Foundation filed Critical Seoul National University R&DB Foundation
Publication of WO2024167347A1 publication Critical patent/WO2024167347A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Images

Classifications

    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/80—Constructional details
    • H10K50/805—Electrodes
    • G—PHYSICS
    • G06—COMPUTING OR CALCULATING; COUNTING
    • G06F—ELECTRIC DIGITAL DATA PROCESSING
    • G06F3/00—Input arrangements for transferring data to be processed into a form capable of being handled by the computer; Output arrangements for transferring data from processing unit to output unit, e.g. interface arrangements
    • G06F3/01—Input arrangements or combined input and output arrangements for interaction between user and computer
    • G—PHYSICS
    • G06—COMPUTING OR CALCULATING; COUNTING
    • G06F—ELECTRIC DIGITAL DATA PROCESSING
    • G06F3/00—Input arrangements for transferring data to be processed into a form capable of being handled by the computer; Output arrangements for transferring data from processing unit to output unit, e.g. interface arrangements
    • G06F3/14—Digital output to display device ; Cooperation and interconnection of the display device with other functional units
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/20—Conductive material dispersed in non-conductive organic material
    • H01B1/22—Conductive material dispersed in non-conductive organic material the conductive material comprising metals or alloys
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B13/00—Apparatus or processes specially adapted for manufacturing conductors or cables
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B5/00—Non-insulated conductors or conductive bodies characterised by their form
    • H01B5/14—Non-insulated conductors or conductive bodies characterised by their form comprising conductive layers or films on insulating-supports
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers
    • H10K50/12—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers comprising dopants
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/17—Carrier injection layers
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
    • H10K71/10—Deposition of organic active material
    • H10K71/12—Deposition of organic active material using liquid deposition, e.g. spin coating
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
    • H10K71/40—Thermal treatment, e.g. annealing in the presence of a solvent vapour
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
    • H10K71/60—Forming conductive regions or layers, e.g. electrodes
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
    • H10K71/80—Manufacture or treatment specially adapted for the organic devices covered by this subclass using temporary substrates
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K77/00—Constructional details of devices covered by this subclass and not covered by groups H10K10/80, H10K30/80, H10K50/80 or H10K59/80
    • H10K77/10—Substrates, e.g. flexible substrates
    • H10K77/111—Flexible substrates
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K2101/00—Properties of the organic materials covered by group H10K85/00
    • H10K2101/20—Delayed fluorescence emission
    • H10K2101/25—Delayed fluorescence emission using exciplex
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy
    • Y02E10/549—Organic PV cells

Definitions

  • the present invention relates to a stretchable electrode, a stretchable organic light-emitting device including the same, and a method for manufacturing the stretchable electrode and the stretchable organic light-emitting device.
  • OLEDs organic light emitting diodes
  • TADF thermally activated delayed fluorescence
  • conductive two-dimensional materials By applying a two-dimensional material to the surface of a conductive nanowire and then embedding it together with the surface of an elastomer, the work function control, two-dimensional electrical contact, and elasticity can be secured simultaneously, thereby solving the problems of existing stretchable electrodes.
  • Such approaches include graphene, reduced graphene oxide (RGO), and MXene.
  • RGO reduced graphene oxide
  • MXene MXene
  • graphene has the disadvantage of being expensive when manufactured by the chemical vapor deposition (CVD) method.
  • CVD chemical vapor deposition
  • the surface of RGO can be functionalized to improve the solution processability, it is difficult to completely replace other conductive two-dimensional materials in terms of conductivity and permeability.
  • MXene is considered the most desirable solution-processable two-dimensional material with high conductivity.
  • MXene has the advantage of being chemically exfoliated, but the stability issue of MXene itself must be solved in order to apply it to the solution process. This problem is caused by the fact that water molecules (approximately 0.27 nm) can easily penetrate the interlayer spacing (d-spacing) of the MXene flakes. Therefore, it is necessary to prevent the MXene d-spacing from increasing during the solution process and to adjust it to be smaller than the size of water molecules to solve the problem of electrode peeling.
  • the first technical task of the present invention is to provide a stretchable electrode capable of efficient charge and hole injection and having high electrical conductivity and light transmittance.
  • the second technical task of the present invention is to provide a stretchable organic light-emitting device with high luminous efficiency.
  • the third technical task of the present invention is to provide a manufacturing method capable of manufacturing a stretchable organic light-emitting device with a simple process and high luminous efficiency.
  • One embodiment of the present invention provides a stretchable electrode including a substrate layer including an elastomer; a conductive layer including conductive nanowires at least partially embedded in the substrate layer; and a contact layer positioned on the conductive layer and including MXene, wherein an outer peripheral surface of the contact layer is surrounded by the substrate layer; wherein the interlayer spacing (d-spacing) of the MXene is 1.01 nm to 1.27 nm.
  • Another embodiment of the present invention provides a stretchable organic light-emitting device including a cathode, an anode facing the cathode, a stretchable light-emitting layer positioned between the cathode and the anode, and a stretchable hole injection layer positioned between the anode and the stretchable light-emitting layer, wherein the cathode and the anode are stretchable electrodes.
  • Another embodiment of the present invention provides a method for manufacturing the stretchable organic light-emitting device, comprising the steps of: preparing the stretchable electrode; forming a stretchable hole injection layer by coating a solution for forming a stretchable hole injection layer on the stretchable electrode; forming a stretchable organic light-emitting layer by coating a solution for forming a stretchable organic light-emitting layer on the stretchable hole injection layer; and positioning the stretchable electrode on the stretchable organic light-emitting layer and performing a heat treatment.
  • the step of preparing the above stretchable electrode may include: a step of forming a contact layer by coating a solution containing MXene on a substrate; a step of heat-treating the contact layer to adjust the interlayer spacing (d-spacing) of the MXene to 1.01 nm to 1.27 nm; a step of forming a conductive layer by coating a solution containing conductive nanowires on the heat-treated contact layer; a step of forming a substrate layer by coating a solution containing an elastomer on the conductive layer and obtaining a laminate; and a step of separating the substrate from the laminate.
  • a stretchable electrode according to one embodiment of the present invention can have a work function that can be adjusted and a low change in resistance due to stretching.
  • a stretchable electrode according to one embodiment of the present invention has excellent moisture stability and may be suitable for a solution process.
  • a stretchable organic light-emitting device has high luminous efficiency and satisfactory elasticity.
  • a manufacturing method according to one embodiment of the present invention is simple in process and can manufacture a stretchable organic light-emitting device with high luminous efficiency.
  • Figures 1a to 1d are cross-sectional views of a stretchable electrode according to one embodiment of the present invention.
  • FIG. 2 is a diagram schematically showing a charge transport path in a stretchable electrode according to one embodiment of the present invention.
  • Figure 3 is a schematic diagram showing a top view of a contact layer including a maxene, a conductive nanowire, and a maxene binder located at the interface.
  • FIG. 4 is a cross-sectional view of an actuator element using a stretchable electrode according to one embodiment of the present invention.
  • FIG. 5 is a cross-sectional view of a stretchable organic light-emitting device according to one embodiment of the present invention.
  • FIG. 6 is a cross-sectional view of a self-operating stretchable organic light-emitting device further including a third electrode and an electrolyte.
  • FIG. 7 is a drawing comparing various characteristics of a stretchable organic light-emitting device capable of self-operation according to one embodiment of the present invention and a conventional method of changing color in response to an external stimulus.
  • Figure 8 is a diagram illustrating the mechanism by which energy transfer occurs from a co-host forming an exciplex to a phosphorescent dopant.
  • FIG. 9 is a drawing showing an example of a material of a stretchable light-emitting layer according to one embodiment of the present invention.
  • Figure 10 is an atomic force microscope (AFM) image of a contact layer (Mxene) including MXene, silver nanowires (Mxene/AgNW) formed on the contact layer, and a MXene binder (Mxene/AgNW/binder) located at the interface of the MXene and silver nanowires, taken during the manufacturing process of Example 1.
  • AFM atomic force microscope
  • Figure 11 is a diagram showing Raman spectra for the electrodes and SEBS manufactured in Example 1 and Reference Example 1.
  • Figure 12 is a drawing showing an XRD graph for the electrodes manufactured in Example 1 and Reference Example 1.
  • Figure 13 is a diagram showing O 1s XPS spectra for the electrodes manufactured in Example 1 and Reference Example 1.
  • Figure 14 is a diagram showing FT-IR spectra for the electrodes of Example 1, Reference Example 1, and Comparative Example 2.
  • Figure 15 is a drawing showing the results of a hydration stability experiment on electrodes manufactured in Example 1 and Comparative Example 1.
  • Figure 16 is an AFM image of the contact layer including MXene after DI water coating for the electrodes manufactured in Example 1 and Comparative Example 1.
  • FIG. 17 is a diagram showing the electrical conductivity and carrier mobility of the electrodes of Example 1, Example 2, and Reference Examples 1 to 3.
  • Figure 18 is a diagram showing the light transmittance and surface resistance (Rs) at 550 nm of the electrodes of Examples 1, 3, and 4.
  • Figure 19 is a diagram showing the work function of the electrodes of Examples 1, 3, 4, and 5.
  • Figure 20a is a drawing showing the results of a static stretching experiment on the electrodes of Example 1, Example 2, and Comparative Example 2.
  • Figure 20b is a diagram showing the results of a cycling elongation experiment on the electrodes of Example 1 and Comparative Example 2.
  • Figure 21 is an AFM image of the maxine layer of the stretchable electrode of Example 1 before stretching, at the time of stretching to an elongation of 40%, and after recovery.
  • Figure 22a is a diagram showing the results of Magneto-PL analysis of a TADF-based stretchable emitting layer (4CzIPN:PU) and a phosphorescent-based stretchable emitting layer (Ir(ppy) 2 acac:PU).
  • Figure 22b is a diagram showing the results of TRPL analysis of a TADF-based stretchable emitting layer (4CzIPN:PU) and a phosphorescent-based stretchable emitting layer (Ir(ppy) 2 acac:PU).
  • Figure 23 is an atomic force microscope image of a stretchable light-emitting layer comprising thermoplastic polyurethane and SEBS elastomer as a matrix of the light-emitting layer.
  • FIG. 24 is a photograph taken when applying tensile strain and torsional strain to a phosphorescent-based stretchable light-emitting layer deposited on a SEBS elastomer substrate, and an optical microscope image taken when the tensile strain ( ⁇ ) is 0%, 100%, and 200%.
  • Figure 25a is a drawing showing the results of XPS analysis and UPS analysis according to the depth of a stretchable hole injection layer manufactured using the solution of Manufacturing Example 4.
  • Figure 25b is a diagram showing the work function and F 1s atom content according to the depth of a stretchable hole injection layer manufactured using the solution of Manufacturing Example 4.
  • Figure 26 is a diagram schematically showing the energy band of the stretchable organic light-emitting device manufactured in Example 7.
  • Figure 27 is a diagram showing the current density, luminance, external quantum efficiency (EQE), and current efficiency of the stretchable organic light-emitting device manufactured in Example 7.
  • a and/or B means “A and B, or A or B.”
  • actuator means a device that converts electrical energy into mechanical energy to enable mechanical motion.
  • stretchable electrodes are required to have both mechanical elasticity and high electrical conductivity.
  • stretchable electrodes are required to have not only mechanical elasticity and high electrical conductivity, but also transparency, an electrode work function that is controllable, and efficient charge and hole injection.
  • One embodiment of the present invention provides a stretchable electrode including a substrate layer including an elastomer; a conductive layer including conductive nanowires at least partially embedded in the substrate layer; and a contact layer positioned on the conductive layer and including MXene, wherein an outer peripheral surface of the contact layer is surrounded by the substrate layer; wherein the interlayer spacing (d-spacing) of the MXene is 1.01 nm to 1.27 nm.
  • a stretchable electrode according to one embodiment of the present invention includes a maxene as a contact layer, the work function of the electrode can be easily controlled through surface modification by substitution of functional groups on the surface of the maxene.
  • a stretchable electrode according to an embodiment of the present invention may have a low change in resistance due to stretching, and may have high electrical conductivity and carrier mobility. Specifically, a stretchable electrode according to an embodiment of the present invention may have a resistance change rate calculated by Equation 1 below of 100% or less when the tensile strain of the stretchable electrode is 40%. A stretchable electrode according to an embodiment of the present invention may have a resistance change rate calculated by Equation 1 below of 300% or less when the tensile strain is 60%.
  • Resistance change rate (%) [(RR 0 )/R 0 ] ⁇ 100 (The above R 0 is a resistance value measured for a stretchable electrode that has not undergone tensile deformation, and the above R is a resistance value measured for a stretchable electrode that has undergone tensile deformation.)
  • a stretchable electrode according to one embodiment of the present invention has excellent moisture stability and is suitable for a solution process since water molecules cannot be inserted between the layers of the MXene since the interlayer spacing (d-spacing) of the MXene is 1.01 nm to 1.27 nm.
  • the interlayer spacing of the MXene included in the above contact layer can be measured through X-ray diffraction (XRD) analysis. More specifically, the interlayer spacing of the MXene included in the above contact layer can be calculated through the 2 theta ( ⁇ ) value of the (002) peak in the XRD spectrum of the MXene and Bragg's Law expressed by the following mathematical equation 1.
  • d is the d-spacing
  • n is a constant
  • ⁇ is the wavelength of the X-ray
  • ⁇ is the angle between the crystal plane and the incident light.
  • the wavelength of the X-ray may be 0.15418 nm.
  • the interlayer spacing of the MXene included in the above contact layer is 1.01 nm to 1.27 nm.
  • the interlayer spacing of the MXene included in the above contact layer may be any one of 1.01 nm, 1.02 nm, 1.03 nm, 1.04 nm, 1.05 nm, 1.06 nm, 1.07 nm, 1.08 nm, 1.09 nm, 1.10 nm, 1.11 nm, 1.12 nm, 1.13 nm, 1.14 nm, 1.15 nm, 1.16 nm, 1.17 nm, 1.18 nm, 1.19 nm, 1.20 nm, 1.21 nm, 1.22 nm, 1.23 nm, 1.24 nm, 1.25 nm, 1.26 nm, and 1.27 nm.
  • the interlayer spacing of the MXene included in the contact layer may be 1.03 nm to 1.20 nm.
  • the solution processability of the contact layer is improved, and a stretchable electrode including the same can be applied to a light-emitting diode manufactured by a solution process.
  • the interlayer spacing of the MXene included in the above contact layer can be controlled by applying heat to the MXene and removing water molecules trapped between the MXene layers. More specifically, the interlayer spacing of the MXene included in the contact layer can be controlled within the above-described range through methods such as heat treatment using a hot plate in a nitrogen or Ar atmosphere, heat treatment using a vacuum oven, or heat treatment using a hot plate in air for the contact layer including the MXene.
  • the heat treatment temperature may be 100°C to 200°C.
  • it may be 100°C, 105°C, 110°C, 115°C, 120°C, 125°C, 130°C, 135°C, 140°C, 145°C, 150°C, 155°C, 160°C, 165°C, 170°C, 175°C, 180°C, 185°C, 190°C, 195°C, 200°C.
  • it may be 120°C or higher and 150°C.
  • the heat treatment time may be from 5 minutes to 60 minutes.
  • Figures 1a to 1d are cross-sectional views of a stretchable electrode according to one embodiment of the present invention.
  • the stretchable electrode (10) has a structure including a substrate layer (03) including an elastomer (022); a conductive layer (02) including conductive nanowires (021) at least partially embedded in the substrate layer (03); and a contact layer (01) positioned on the conductive layer (02) and including MXene, wherein an outer peripheral surface of the contact layer (01) is surrounded by the substrate layer (03).
  • the stretchable electrode according to one embodiment of the present invention has excellent elasticity by having the above-described structure, and may have low resistance change due to stretching.
  • the stretchable electrode (10) may have a structure as shown in Fig. 1c by removing all or part of the side surface of the substrate layer (03). The size adjustment process does not affect the elasticity, surface resistance, and transmittance of the electrode.
  • the stretchable electrode (10) may further include a work function adjusting layer (04) on the contact layer (01).
  • a work function adjusting layer By further including the work function adjusting layer, it may be possible to adjust the work function of the electrode.
  • the thickness of the substrate layer may be 1 ⁇ m to 1000 ⁇ m.
  • the conductive nanowire at least part of which is embedded in the substrate layer, can be embedded from 1 nm to 1000 nm of the substrate layer surface.
  • it can be embedded from 1 nm, 2 nm, 3 nm, 4 nm, 5 nm, 6 nm, 7 nm, 8 nm, 9 nm, 10 nm, 15 nm, 20 nm, 30 nm, 40 nm, 50 nm, 60 nm, 70 nm, 80 nm, 90 nm, 100 nm, 200 nm, 300 nm, 400 nm, 500 nm, 600 nm, 700 nm, 800 nm, 900 nm, 1000 nm of the substrate layer surface.
  • the thickness of the contact layer including the MXene may be 1 nm to 100 nm. Specifically, the thickness of the contact layer including the MXene may be 2 nm to 80 nm, 2 nm to 75 nm, 2 nm to 50 nm, 2 nm to 30 nm, 2 nm to 20 nm or 2 nm to 10 nm, and preferably 2 to 10 nm.
  • the thickness of the contact layer including the MXene is 2 nm to 10 nm, the transmittance of the stretchable electrode including it may be improved.
  • the composition of the MXene included in the contact layer can be expressed as M n+1 X n or M n+1 X n T x .
  • M is a transition metal
  • X is carbon (C), nitrogen (N) or a combination thereof
  • T x may mean a surface termination including oxide (O), hydroxide (OH), fluoride (F) or a combination thereof
  • n may be an integer from 1 to 4.
  • M and X are not limited to just one type, and multiple elements may be used at the same time.
  • the MXene may include at least one MXene flake having a two-dimensional layered structure.
  • One MXene flake may have a thickness of 1 nm to 5 nm and a size of 1 ⁇ m to 100 ⁇ m.
  • the contact layer including the maxine may have a structure in which the elastomer enters the space between the maxine flakes and is semi-embedded in the substrate layer, or may have a structure in which it is not semi-embedded in the substrate layer.
  • the conductive nanowires can form a conductive network under the contact layer including the MXene. Therefore, when the stretchable electrode is stretched, the distance between the MXene flakes included in the contact layer increases and cracks occur, but the conductive network formed by the conductive nanowires acts as a bridging, so that a conductive path can be maintained even when stretching, so that the change in resistance of the electrode is low and the conductivity of the electrode may not deteriorate even when continuously stretched.
  • the conductive nanowire includes a conductive material such as a conductive metal, a conductive nonmetal, a carbon nanotube (CNT), a metal oxide, a metalloid, or a conductive polymer, and may be a wire-shaped particle having an aspect ratio (length/width) of 10 or more.
  • the conductive nanowire may be a silver nanowire, a copper nanowire, a gold nanowire, a carbon nanotube, a carbon nanoplate, or a metal nanowire coated with a heterometal, but is not particularly limited thereto.
  • the conductive nanowire may include a functional group capable of forming a hydrogen bond on its surface. Since the conductive nanowire includes a functional group capable of forming a hydrogen bond on its surface, it may be adhered to the MXene flake through hydrogen bonding with the MXene binder described below, and may maintain a conductive path through the conductive network without being separated from the MXene flake even when a high level of elongation occurs.
  • FIG. 2 is a diagram schematically showing a charge transport path in a stretchable electrode according to an embodiment of the present invention.
  • charge transport in the stretchable electrode is caused by two types of transport: hopping transport between MXene flakes (2D materials) included in a contact layer and band transport between conductive nanowires (1D materials) under the contact layer. It is known that short-distance charge transport in MXene flakes is dominated by band transport, whereas long-distance charge transport relies on thermally activated hopping, which suggests that hopping charge transport is a rate-limiting factor in long-distance charge transport.
  • the stretchable electrode includes conductive nanowires located under the contact layer, charge transport is caused by not only hopping transport between MXene flakes (2D materials) but also band transport between conductive nanowires (1D materials), so that electrical conductivity and charge mobility can be excellent.
  • the elastomer is a homo copolymer, an alternating copolymer, a random copolymer, a block copolymer, a multiblock copolymer, or at least one selected from the group consisting of polydimethylsiloxane (PDMS), polyurethane (PU), styrene butadiene styrene (SBS), styrene ethylene butylene styrene (SEBS), ecoflex, a hydrogel, an organogel, polyethylene oxide (PEO), polystyrene (PS), polycaprolactone (PCL), polyacrylonitrile (PAN), polymethyl methacrylate (PMMA), polyimide, polyvinylidene fluoride (PVDF), poly(n-vinylcarbazole) (PVK), polyvinyl chloride (PVC), derivatives thereof, and combinations thereof. It may be a graft copolymer. According to one
  • a stretchable electrode according to one embodiment of the present invention may further include a MXene binder positioned at an interface between the MXene and the conductive nanowire and an interface between the conductive nanowires, and bonding the MXene and the conductive nanowire.
  • the MXene binder includes a MXene represented by M n+1 X n T x , wherein M is a transition metal, X is carbon (C), nitrogen (N) or a combination thereof, T x is a surface termination including oxide (O), hydroxide (OH), fluoride (F) or a combination thereof, and n may be an integer from 1 to 4. Since the MXene binder includes a surface termination including oxide (O), hydroxide (OH), fluoride (F) or a combination thereof, adhesion between the MXene included in the contact layer and the conductive nanowire can be achieved through hydrogen bonding.
  • the stretchable electrode according to one embodiment of the present invention further includes the MXene binder, the contact resistance at the interface between the MXene and the conductive nanowire and at the interface between the conductive nanowires can be reduced, and thus the electrical conductivity and elasticity of the stretchable electrode can be improved.
  • FIG. 3 is a schematic diagram showing a top view of a contact layer including MXene, a conductive nanowire, and a MXene binder located at an interface.
  • the MXene binder has surface termination groups such as a fluoride group (-F) or a hydroxide group (-OH) and can form intermolecular interactions such as hydrogen bonding, and the MXene binder is concentrated at the interface where the conductive nanowires intersect each other and the interface where the conductive nanowires come into contact with the contact layer, and can act as a binder that adheres the MXene and the conductive nanowires through hydrogen bonding.
  • the stretchable electrode can control the work function of the electrode by forming a work function control layer by modifying the surface of the contact layer.
  • Charge transfer occurs between the material included in the work function control layer and the MXene included in the contact layer, and thus the electron level changes and the work function of the electrode can change.
  • the work function thermodynamically means an energy level at which electrons can exist with a probability of 1/2.
  • the stretchable electrode can reduce the work function of the electrode by surface-modifying the electrode by applying a material including an electron donating group to the surface of the contact layer, and can increase the work function of the electrode by surface-modifying the electrode by applying a material including an electron withdrawing group.
  • the work function of the stretchable electrode may be 2.0 eV to 7.0 eV.
  • the stretchable electrode may include a range in which the lower value of two numbers selected from 5.4
  • the work function of a stretchable electrode that does not include a work function adjusting layer, i.e., a surface of a contact layer is not modified may be 4.0 eV to 5.0 eV.
  • the work function controlling layer may include at least one selected from the group consisting of polyethylene imine (PEI); polyethyleneimine ethoxylated (PEIE); poly[(9,9-bis(3'-(N,N-dimethylamino)propyl)-2,7-fluorene)-alt-2,7-(9,9-dioctylfluorene)] dibromide (PFN-Br); a polymer compound represented by the following chemical formula 1; and derivatives thereof.
  • PEI polyethylene imine
  • PEIE polyethyleneimine ethoxylated
  • PFN-Br poly[(9,9-bis(3'-(N,N-dimethylamino)propyl)-2,7-fluorene)-alt-2,7-(9,9-dioctylfluorene)] dibromide
  • PPN-Br polymer compound represented by the following chemical formula 1; and derivatives thereof.
  • the work function of the stretchable electrode including the work function controlling layer including the material described above can be 2.0 eV to 4.0 eV.
  • the stretchable electrode including the work function controlling layer including the material described above can be used as a cathode of a stretchable organic light-emitting device described below.
  • Ar 1 and Ar 2 are main chains having a conjugated structure, each independently at least one selected from fluorene, spirofluorene, carbazole, thiophene, phenylene, phenylene vinylene and derivatives thereof, or more specifically, one selected from the following first compound group,
  • n are each independently an integer from 1 to 1,000,000
  • a - is any one selected from SO 3 - , PO 3 2- , and CO 2 - ,
  • C + is one selected from H + , Li + , Na + , K + , Rb + , Cs + , NH4 + ,
  • X is -C n H 2n -O- (n is an integer from 1 to 20)
  • Y is -C n H 2n - (n is an integer from 1 to 20)
  • R 1 and R 2 are each independently bonded to a carbon atom of a substituted or unsubstituted crown ether compound:
  • the polymer compound represented by the chemical formula 1 may be a polymer compound represented by the following chemical formula 2.
  • k, l, m and n are each independently an integer from 1 to 10, the ratio of the number of repeating units a:b satisfies 0.1:0.9 to 1:0, X + is NH 4 + , and R 1 and R 2 are each independently bonded to a carbon of a substituted or unsubstituted crown ether compound.
  • the polymer compound represented by the chemical formula 2 may be a polymer compound represented by the following chemical formula 3.
  • n and m are each independently an integer from 1 to 100.
  • the polymer compound represented by the chemical formula 1 may have a weight average molecular weight of 5,000,000 g/mol or less and 500 g/mol or more.
  • the substituted or unsubstituted crown ether compound may be at least one selected from the following second compound group.
  • the polymer compound represented by the chemical formula 1 may be a polyfluorene-based anionic conjugated polymer, which may be an 18-crown-6 attached poly(fluorene-co-phenylene) sulfonate having tetramethylammonium (TMA + ) as a counter ion.
  • TMA + tetramethylammonium
  • the work function controlling layer may include at least one selected from the group consisting of perfluorinated organic compounds, AuCl 3 , HNO 3 and derivatives thereof.
  • the work function of a stretchable electrode including a work function controlling layer including the above-described material may increase compared to a case where the work function controlling layer is not included.
  • the work function of a stretchable electrode including a work function controlling layer including the above-described material may be 5.0 eV to 7.0 eV.
  • a stretchable electrode including a work function controlling layer including the above-described material can be used as an anode of a stretchable organic light-emitting device to be described later.
  • the perfluorinated organic compound may be, but is not limited to, a perfluorinated alkyl halides, a perfluorinated aryl halide, a fluorochloroalkene, a perfluoroalcohol, a perfluorinated amine, a perfluorocarboxylic acid, a perfluorosulfonic acid or a derivative thereof.
  • the perfluorinated alkyl halide and the perfluorinated aryl halide may be, but are not limited to, trifluoroiodomethane, pentafluoroethyl iodide, perfluorooctyl bromide (perflubron), dichlorodifluoromethane and derivatives thereof.
  • the fluorochloro alkene can be chlorotrifluoroethylene, dichlorodifluoroethylene, and derivatives thereof
  • the perfluorocarboxylic acid can be trifluoroacetic acid, heptafluorobutryric acid, pentafluorobenzoic acid, perfluorooctanoic acid, perfluorononanoic acid, and derivatives thereof.
  • the perfluorosulfonic acid can be triflic acid, perfluorobuanesulfonic acid, perfluorobutane sulfonamide, perfluorooctanesulfonic acid, and derivatives thereof.
  • a stretchable electrode according to one embodiment of the present invention can satisfy a light transmittance of 85% or more and 95% or less, 87% or more and 95% or less, or 90% or more and 95% or less at a wavelength of 550 nm.
  • the stretchable electrode can satisfy transparency by satisfying the above-described range of light transmittance at a wavelength of 550 nm, and can be suitable for application to an organic light-emitting device.
  • a stretchable electrode according to one embodiment of the present invention may have a sheet resistance (Rs) of 40 ⁇ /sq or less, 35 ⁇ /sq or less, or 30 ⁇ /sq or less, or 5 ⁇ /sq or less, and may be 1 ⁇ /sq or more.
  • the stretchable electrode according to one embodiment of the present invention can be used in an actuator element capable of self-operation in addition to the stretchable organic light-emitting element described below. Since MXene is a two-dimensional material, intercalation of ions is possible, and thus the stretchable electrode according to one embodiment of the present invention can be used as an electrode of an actuator element.
  • FIG. 4 is a cross-sectional view of an actuator element using a stretchable electrode according to one embodiment of the present invention.
  • the actuator element (200) includes a first electrode, a second electrode facing the first electrode, and an electrolyte (60) interposed between the first electrode and the second electrode, and the first electrode and the second electrode may be a stretchable electrode (10) according to one embodiment of the present invention.
  • the first electrode and the second electrode may have a polymer added thereto to improve adhesion with the electrolyte (60) material.
  • the first electrode and the second electrode may include a composite material in which a polymer such as PEDOT:PSS is further added to a contact layer including MXene. By adding a polymer to the contact layer, binding characteristics, electrical conductivity, or ion intercalation characteristics can be improved.
  • the electrolyte (60) may include an ionic dielectric material.
  • the ionic dielectric material is characterized in that polarization is formed or separated according to an electrical signal applied to positive and negative ions, and includes, but is not limited to, materials such as metals, ceramics, polymers, semiconductors, and dielectrics that contain ions.
  • the ionic dielectric material is 1-Ethyl-3-methylimidazolium, 1-Butyl-3-methylimidazolium, Methyl-tributylammonium, 1,2,3-Trimethylimidazolium, Methylimidazolium, 1-Ethyl-2,3-dimethylimidazolium, 1-Butyl-2,3-dimethylimidazolium, 1-Dodecyl-3-methylimidazolium, 1-Butyl-1-methylpyrrolidinium, N-Methyl-N-trioctylammonium, N-Butyl-N-methylpyrrolidinium, Triethylsulphonium, Tetraethylammonium, Tetrabutylphosphonium, Methyltrioctylammonium, 3-Methyl-1-propylpyridinium, 1,2-Dimethyl-3-propylimidazolium, 1-Hexyl-3-methylimida
  • Another embodiment of the present invention provides a stretchable organic light-emitting device including a cathode, an anode facing the cathode, a stretchable light-emitting layer positioned between the cathode and the anode, and a stretchable hole injection layer positioned between the anode and the stretchable light-emitting layer, wherein the cathode and the anode are stretchable electrodes.
  • a stretchable organic light-emitting device has high luminous efficiency and satisfactory elasticity.
  • FIG. 5 is a cross-sectional view of a stretchable organic light-emitting device according to one embodiment of the present invention.
  • a stretchable organic light-emitting device (100) includes a cathode (20), an anode (30) facing the cathode (20), a stretchable light-emitting layer (40) positioned between the cathode (20) and the anode (30), and a stretchable hole injection layer (50) positioned between the anode (30) and the stretchable light-emitting layer (40), wherein the cathode and the anode are stretchable electrodes according to one embodiment of the present invention described above.
  • the stretchable organic light-emitting device (100) may further include at least one of an electron injection layer (not shown) and an electron transport layer (not shown) between the cathode (20) and the stretchable light-emitting layer (40), as needed, and may further include a hole transport layer (not shown) between the stretchable light-emitting layer (40) and the stretchable hole injection layer (50).
  • a stretchable organic light-emitting device may further include a third electrode and an electrolyte, and by further including the third electrode and an electrolyte, a self-operating stretchable organic light-emitting device capable of simultaneously outputting an electrical signal in the form of light and movement may be provided.
  • FIG. 6 is a cross-sectional view of a self-operating stretchable organic light-emitting device further including a third electrode and an electrolyte.
  • the stretchable organic light-emitting device (300) capable of self-operation may include a stretchable electrode (10) as a third electrode facing the anode (30) in the stretchable organic light-emitting device according to the present invention, and an electrolyte (60) interposed between the stretchable electrode (10) and the anode (30).
  • the stretchable electrode as the third electrode may be a stretchable electrode according to one embodiment of the present invention.
  • the stretchable organic light-emitting device capable of self-operation can emit light by receiving an electrical signal, and at the same time, can generate its own mechanical movement. That is, the stretchable organic light-emitting device capable of self-operation can simultaneously implement light, movement, or light and movement as an actuator and a display.
  • the stretchable organic light-emitting device capable of self-operation can have a low driving voltage, be DC-driven, and have high electric luminescence efficiency.
  • the stretchable organic light-emitting device capable of self-motion can be used in soft robots, neural prosthetics, and prosthetic forms by amplifying external micro-stimulation signals and outputting them as movement and light to mimic the functions of indicating danger signals and avoiding danger.
  • FIG. 7 is a drawing comparing various characteristics of a stretchable organic light-emitting device capable of self-operation according to one embodiment of the present invention and a conventional method of changing color in response to an external stimulus.
  • a passive color conversion system Passive method
  • Passive method a passive color conversion system such as that disclosed in a paper (ACS Nano 2017, 11, 11350/ Adv. Func. Mater. 2019, 29, 1806383/ Adv. Func. Mater. 2018, 28, 1801847/ Proc. Natl. Acad. Sci. U. S. A.
  • a stretchable organic light-emitting device capable of self-operation may have a lower driving voltage, be DC-driven, and have better electroluminescence efficiency compared to a conventional multimodal display device.
  • the above stretchable light-emitting layer (40) plays a role in generating light by forming excitons through the combination of holes (h) flowing in from the anode and electrons (e) flowing in from the cathode, and emitting light as the excitons transition to the ground state.
  • the stretchable light-emitting layer may include a thermoplastic polyurethane matrix; a co-host dispersed in the thermoplastic polyurethane matrix and forming an exciplex; and a phosphorescent dopant dispersed in the thermoplastic polyurethane matrix.
  • a stretchable organic light-emitting device can maintain a high level of luminous efficiency even when stretched by including the stretchable light-emitting layer, and is mechanically strong and can withstand tensile strain of 200%.
  • non-radiative triplets In order to efficiently collect triplets in the stretchable light-emitting layer, non-radiative triplets must be converted into radiative singlets or triplets through a spin-flip process.
  • a stretchable organic light-emitting device using a conventional TADF type light-emitting layer when mechanical deformation due to stretching is applied, the intermolecular distance included in the light-emitting layer may change, and thus the spin-orbit coupling (SOC) may decrease.
  • SOC spin-orbit coupling
  • the decrease in SOC due to stretching interferes with the spin-flip process, which ultimately results in a decrease in triplet collection efficiency.
  • the stretchable light-emitting layer includes a phosphorescent dopant having a strong SOC dispersed in the thermoplastic polyurethane matrix, and thus the triplet collection efficiency can be maintained high even under mechanical deformation due to stretching.
  • FIG. 8 is a diagram showing a mechanism for energy transfer from a co-host forming an exciplex to a phosphorescent dopant.
  • a co-host composed of an electron-transporting host (TPBi) and a hole-transporting host (TCTA) can form an exciplex, and the energy of the exciplex is transferred to the phosphorescent dopant (Ir(ppy)2acac) in a Foster or Dexter manner.
  • a stretchable light-emitting layer capable of maintaining a high level of luminescence efficiency even during stretching can be provided.
  • the stretchable light-emitting layer includes a co-host forming an exciplex, a recombination region is expanded, thereby achieving balanced charge carrier injection.
  • the co-host forming the exciplex may be formed by a combination of an electron-transporting host and a hole-transporting host.
  • the above electron transport host may include a known electron transport material.
  • the electron transport host is a quinoline derivative, particularly tris(8-hydroxyquinoline) aluminum (Alq3), bis(2-methyl-8-quinolinolate)-4-(phenylphenolato)aluminium (Balq), bis(10-hydroxybenzo[h]quinolinato)-beryllium (Bebq2), 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline (BCP), 4,7-diphenyl-1,10-phenanthroline.
  • Alq3 tris(8-hydroxyquinoline) aluminum
  • Alq bis(2-methyl-8-quinolinolate)-4-(phenylphenolato)aluminium
  • Bebq2 bis(10-hydroxybenzo[h]quinolinato)-beryllium
  • BCP 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline
  • BCP 2,9-dimethyl-4,7-dip
  • the above hole transport host may include a known hole transport material.
  • the hole transport host may be selected from the group consisting of 1,3-bis(carbazol-9-yl)benzene (MCP), 1,3,5-tris(carbazol-9-yl)benzene (TCP), 4,4',4"-tris(carbazol-9-yl)triphenylamine (TCTA), 4,4'-bis(carbazol-9-yl)biphenyl (CBP), N,N'-bis(naphthalen-1-yl)-N,N'-bis(phenyl)benzidine (N,N'-bis(naphthalen-1-yl)-N,N'-bis(phenyl)benzidine.
  • MCP 1,3-bis(carbazol-9-yl)benzene
  • TCP 1,3,5-tris(carbazol-9-yl)benzene
  • TCTA 4,4',4"-tris(carbazol-9-yl)triphenylamine
  • NPB N,N'-bis(naphthalen-2-yl)-N,N'-bis(phenyl)-benzidine
  • ⁇ -NPB N,N'-bis(naphthalen-1-yl)-N,N'-bis(phenyl)-2,2'-dimethylbenzidine
  • ⁇ -NPD Di-[4-(N,N-ditolyl-amino)-phenyl]cyclohexane
  • TAPC N,N,N',N'-tetra-naphthalen-2-yl-benzidine
  • ⁇ -TN N,N,N',N'-tetra-naphthalen-2-yl-benzidine
  • the combination of the hole-transporting host and the electron-transporting host forming the above exciplex can be, for example, mCP:B3PYMPM, TCTA:B3PYMPM, TCTA:TPBi, TCTA:3TPYMB, TCTA:BmPyPB, TCTA:BSFM, CBP:B3PYMPM or NPB:BSFM, and preferably, a combination of TCTA:TPBi.
  • the face-to-face alignment of the planar structures of TPBi and TCTA can minimize a change in spin-orbit coupling (SOC) of the exciplex depending on a change in the concentration of the thermoplastic polyurethane matrix.
  • SOC spin-orbit coupling
  • the stretchable light-emitting layer includes a thermoplastic polyurethane matrix
  • the photoluminescence (PL) intensity and lifespan of the light-emitting layer can be improved due to trap dilution, and since the co-host and phosphorescent dopant dispersed in the matrix are well dispersed and do not phase separate, a high level of light-emitting efficiency can be maintained even during stretching.
  • the phosphorescent dopant may have a triplet energy lower than the triplet energy of the exciplex.
  • the phosphorescent dopant may be a complex of a heavy metal such as iridium (Ir), platinum (Pt), osmium (Os), ruthenium (II), or rhenium (Re) and an organic ligand.
  • the phosphorescent dopant is (Ir(ppy)2acac), Ir(ppy)3, Ir(ppy)2(bpmp), Ir(3mppy)3, Ir(dmppy-pro)2tmd, Ir(npy) 2acac, Ir(mppy)3, fac-Ir(ppy)3, FIr4mpic, Ir(Fppy)3, Ir(tfpd)2pic, FK306, FCNIrPic, fac-Ir(dpbic)3, mer-Ir(pmi)3, FIrN4, Bepp2, mer-Ir(pmb)3, fac-Ir(Pmb)3, FIr6 (Bis(2,4-difluorophenylpyridinato)-tetrakis(1-pyrazolyl)borate iridium(III)), Ir(piq-dm) 2(acac); Ir(dmpq)2(acac), Eu(TTA)
  • FIG. 9 is a drawing showing an example of a material of a stretchable light-emitting layer according to one embodiment of the present invention.
  • the stretchable hole injection layer may include a surfactant, a conductive polymer, and a perfluorinated compound. Since the stretchable hole injection layer includes the surfactant, the conductive polymer, and the perfluorinated compound, the stretchable hole injection layer may have a work function that gradually increases in the direction of the stretchable organic light-emitting layer, and may achieve excellent elasticity.
  • a self-assembled layer in which fluorine atoms are concentrated is formed near the surface of the stretchable hole injection layer, and as the fluorine content decreases in the thickness direction of the stretchable hole injection layer, the work function may gradually change, and the surfactant may act as a plasticizer to reduce the glass transition temperature of the stretchable hole injection layer material, thereby ensuring elasticity.
  • the conductive polymer may include materials commonly used in the art, and those described above may be used as examples of the conductive polymer included in the conductive material layer of the stretchable electrode.
  • the conductive polymer may include PEDOT:PSS (poly(3,4-ethylenedioxythiophene) polystyrene sulfonate).
  • PEDOT:PSS poly(3,4-ethylenedioxythiophene) polystyrene sulfonate
  • phase separation between PEDOT and PSS is induced by the surfactant, and the elasticity of the stretchable hole injection layer may be further improved.
  • the perfluorinated compound may be, but is not limited to, a perfluorinated alkyl halide, a perfluorinated aryl halide, a fluorochloroalkene, a perfluoroalcohol, a perfluorinated amine, a perfluorocarboxylic acid, a perfluorosulfonic acid or a derivative thereof.
  • the perfluorinated alkyl halide and the perfluorinated aryl halide may be, but are not limited to, trifluoroiodomethane, pentafluoroethyl iodide, perfluorooctyl bromide (perflubron), dichlorodifluoromethane and derivatives thereof.
  • the fluorochloro alkene can be chlorotrifluoroethylene, dichlorodifluoroethylene, and derivatives thereof
  • the perfluorocarboxylic acid can be trifluoroacetic acid, heptafluorobutryric acid, pentafluorobenzoic acid, perfluorooctanoic acid, perfluorononanoic acid, and derivatives thereof.
  • the perfluorosulfonic acid can be triflic acid, perfluorobuanesulfonic acid, perfluorobutane sulfonamide, perfluorooctanesulfonic acid, and derivatives thereof.
  • the surfactant is an amphipathic substance having two opposing functional groups, hydrophilic and hydrophobic, in the same molecule, and can play a role in exhibiting various physical phenomena by being adsorbed at the interface between a liquid and a gas, a liquid and a liquid, or a liquid and a solid.
  • the role of the surfactant can be to lower surface tension, emulsify, improve wettability, foamability, or solubilize.
  • the surfactant binds to the surface of a nanoparticle through a coordination bond and acts as a ligand, the dispersibility of the nanoparticle can be increased.
  • surfactants include anionic surfactants (containing sulfates (e.g., ammonium lauryl sulfate, sodium lauryl sulfate, sodium dodecyl sulfate, sodium laureth sulfate, sodium myreth sulfate), sulfonates (e.g., dioctyl sodium sulfosuccinate, perfluorooctanesulfonate, perfluorobutanesulfonate, linear alkylbenzne sulfates), phosphate esters, carboxylates (e.g., sodium stearate, sodium lauroyl sarcosinate, perfluorononanoate, perfluorooctanoate)), cationic surfactants (containing primary, secondary, tertiary, and quatenary ammonium cations), and quaternary ammonium cations such as Benzalkonium chloride, Dimethyldio
  • nonionic surfactants include zwitterionic or amphoteric surfactants, which have both hydrophobic and hydrophobic properties, and long chain alcohols such as fatty alcohols cetyl alcohol, stearyl alcohol, cetostearyl alcohol (consisting predominantly of cetyl and stearyl alcohols), and oleyl alcohol.
  • the nonionic surfactant may include one selected from the group consisting of polysorbate, polyethylene glycol (PEG), Nonoxynol-9, octoxynol-9 (Triton X-100, Octoxynol-9), alkyl polyglucoside (APG), ethylene oxide/propylene oxide copolymers, derivatives thereof, and combinations thereof.
  • product names of compounds that can be used as the nonionic surfactant include Zonyl FS-300, Zonyl FSN, Zonyl FSN-100, Zonyl FSO-100, ACH SN104, Andisil SP 19, ECO Tween 20, ECO Tween 40, ECO Tween 60, ECO Tween 80, ECO Tween 85, Span, Triton X-100, Triton X-102, Triton X-114, Triton X-405, and Triton X-4.
  • Another embodiment of the present invention provides a method for manufacturing the stretchable organic light-emitting device, comprising the steps of: preparing the stretchable electrode; forming a stretchable hole injection layer by coating a solution for forming a stretchable hole injection layer on the stretchable electrode; forming a stretchable organic light-emitting layer by coating a solution for forming a stretchable organic light-emitting layer on the stretchable hole injection layer; and positioning the stretchable electrode on the stretchable organic light-emitting layer and performing a heat treatment.
  • the step of preparing the above stretchable electrode may include: a step of forming a contact layer by coating a solution containing MXene on a substrate; a step of heat-treating the contact layer to adjust the interlayer spacing (d-spacing) of the MXene to 1.01 nm to 1.27 nm; a step of forming a conductive layer by coating a solution containing conductive nanowires on the heat-treated contact layer; a step of forming a substrate layer by coating a solution containing an elastomer on the conductive layer and obtaining a laminate; and a step of separating the substrate from the laminate.
  • the electrode manufactured by the step of preparing the above stretchable electrode including the step of heat-treating the contact layer to adjust the interlayer spacing (d-spacing) of the MXene to 1.01 nm to 1.27 nm has moisture stability and does not deteriorate or damage the electrode in a moisture environment, so that it can be suitable for use in a solution process.
  • the temperature for heat-treating the contact layer may be 100°C to 200°C.
  • it may be 100°C, 105°C, 110°C, 115°C, 120°C, 125°C, 130°C, 135°C, 140°C, 145°C, 150°C, 155°C, 160°C, 165°C, 170°C, 175°C, 180°C, 185°C, 190°C, 195°C, 200°C.
  • it may be 120°C or higher and 150°C.
  • the manufacturing method according to the present invention is a solution process, and each solution used may contain an appropriate solvent for the above-described components and each component part of the stretchable organic light-emitting device and stretchable electrode according to the present invention.
  • the concentration of the MXene solution used in the step of forming the contact layer may be 4 mg/mL to 15 mg/mL.
  • the concentration of the MXene solution may have a range in which the lower value of two numbers selected from 4 mg/mL, 5 mg/mL, 6 mg/mL, 7 mg/mL, 8 mg/mL, 9 mg/mL, 10 mg/mL, 11 mg/mL, 12 mg/mL, 13 mg/mL, 14 mg/mL and 15 mg/mL is the lower limit and the higher value is the upper limit.
  • the concentration of the MXene solution satisfies the above-described range, a film-shaped contact layer can be formed, and the conductivity of the contact layer can be excellent.
  • the step of preparing the stretchable electrode may further include a step of forming a MXene binder by coating a diluted MXene solution on the conductive layer before the step of forming the substrate layer and obtaining a laminate.
  • the concentration of the diluted maxine solution may be 0.1 mg/mL or more and 3 mg/mL or less.
  • the concentration of the diluted MXene solution is 0.1 mg/mL, 0.2 mg/mL, 0.3 mg/mL, 0.4 mg/mL, 0.5 mg/mL, 0.6 mg/mL, 0.7 mg/mL, 0.8 mg/mL, 0.9 mg/mL, 1.0 mg/mL, 1.1 mg/mL, 1.2 mg/mL, 1.3 mg/mL, 1.4 mg/mL and It can have a range where the lower value of the two numbers selected from 3.0 mg/mL is the lower limit and the higher value is the upper limit.
  • the method for coating the solution is not particularly limited, and may be, for example, spin-coating, drop casting, or ink-jet printing.
  • the step of forming the contact layer may be preferably performed by spin coating.
  • the step of forming the contact layer is performed by spin coating, water molecules that may be included between the layers of the MXene are removed, so that the interlayer spacing of the MXene can be well controlled in the step of heat-treating the contact layer.
  • Another embodiment of the present invention can provide a bio-neuromimetic system using a stretchable organic light-emitting device according to the present invention.
  • the stretchable organic light-emitting device according to the present invention can be applied as an output device of a bio-neuromimetic system.
  • the above-described bionic neuromimetic system may include a sensory nerve device, a motor nerve device, and an artificial synaptic element.
  • the artificial synaptic element receives a presynaptic signal and outputs a postsynaptic signal, and processes a sensory signal from at least one artificial sensor or biological organ to control and stimulate at least one artificial motor organ or biological organ.
  • a bio-neuromimetic system using a stretchable organic light-emitting device capable of self-movement according to the present invention that can simultaneously output electrical signals in the form of light and movement can amplify external micro-stimulation signals and output them as movement and light to mimic the functions of indicating danger signals and avoiding danger, and thus can be used in soft robots, neural prosthetics, and prosthetic forms.
  • Korean Patent Publication No. 10-2023-0162561, Korean Registration Patent No. 10-2191817, and Korean Registration Patent No. 10-2246807 may be included in the present invention.
  • MXene (Ti 3 C 2 T x ) was synthesized using the method described in the previous literature ( Huanyu Zhou et al., Adv. Mater. 2022, 34, 2206377 ).
  • Cn6-FPS (18-crown-6 attached poly(fluorene-co-phenylene) sulfonate with tetramethylammonium (TMA+) counterions) represented by the following chemical formula was synthesized using the method described in the previous literature ( Huanyu Zhou et al., Adv. Mater. 2022, 34, 2203040 ).
  • Example 1 Fabrication of MXene-contact stretchable electrodes (MCSE)
  • a glass substrate was ultrasonically treated using acetone and isopropyl alcohol (IPA) as solvents, and the glass substrate was treated with ultraviolet light (UV Ozone) for 15 minutes.
  • IPA isopropyl alcohol
  • UV Ozone ultraviolet light
  • a solution (8 mg/mL in DI water) containing MXene prepared in Manufacturing Example 1 was applied so as to cover the surface of the glass substrate, and waited for 3 minutes for self-assembly.
  • spin-coating was performed at 2000 rpm for 60 seconds, and spin-coating was performed at 6000 rpm for 90 seconds to evaporate the solvent of the MXene solution, thereby forming a contact layer containing MXene on the glass substrate.
  • the glass substrate coated with the above contact layer was heat-treated at a temperature of 150° C. for 2 hours in a glove box under a nitrogen atmosphere to reduce the interlayer spacing of the MXene included in the contact layer.
  • AgNWs silver nanowires
  • IPA isopropyl alcohol
  • heat treatment was performed at 120 °C for 10 min in an air atmosphere to promote interactions at both the AgNW/AgNW and AgNW/MXene interfaces.
  • a diluted MXene solution (0.5 mg/mL in DI water) containing the MXene of Preparation Example 1 was applied onto the conductive layer and spin-coated at 2000 rpm for 60 s to form a MXene binder that is located at the interface between AgNW/AgNW and AgNW/MXene and bonds AgNW/AgNW and AgNW/MXene through hydrogen bonding.
  • the laminate of glass substrate-MXene contact layer-AgNW conductive layer-SEBS substrate layer was immersed in water to separate the glass substrate from the laminate, thereby fabricating a MXene-contact stretchable electrode.
  • a MXene-contacted stretchable electrode was prepared in the same manner as in Example 1, except that the MXene binder was not formed.
  • Example 3 Fabrication of MXene-contact stretchable electrodes for anode application (A-MCSE) with increased work function
  • PFSA perfluorosulfonic acid
  • Example 4 Preparation of MXene-contact stretchable electrodes for cathode application (C-MCSE) with reduced work function
  • a polyethyleneimine (PEI, Sigma-Aldrich) solution (0.5 wt% in 2-methoxyethanol) was spin-coated at 3000 rpm for 60 seconds on the contact layer of MCSE prepared in Example 1, followed by heat treatment at 90 °C for 5 minutes to form a work function control layer.
  • PEI polyethyleneimine
  • Example 5 Fabrication of MXene-contact stretchable electrodes for cathode application (C-MCSE) with reduced work function
  • C-MCSE having a low work function for cathode use
  • a solution containing Cn6-FPS of Preparation Example 2 (1.5 mg/mL in 2-methoxyethanol) was spin-coated at 3000 rpm for 60 seconds on the contact layer of MCSE prepared in Example 1, followed by heat treatment at 90° C. for 5 minutes to form a work function control layer.
  • Example 1 prior to forming a contact layer including MXene, a photoresist pattern layer was formed on a glass substrate as follows, and a patterned MXene-contact stretchable electrode was manufactured through the same method as in Example 1, except that the pattern layer was removed by immersing in acetone for 30 seconds prior to separating the electrode laminate from the glass substrate.
  • a positive photoresist PR, AZ GXR-601
  • PR positive photoresist
  • the photoresist layer was soft baked at 120 °C for 3 minutes to remove the solvent and improve adhesion to the glass substrate.
  • UV was irradiated to the substrate to form a bank structure for the subsequent patterning process, and the substrate was immersed in a developer (AZ 300 MIF) for 30 s.
  • the substrate was thoroughly rinsed with deionized water (DIW) to remove excess developer, and hard baked at 120 °C for 3 minutes to ensure complete cross-linking of the photoresist, to form a photoresist pattern layer on the glass substrate.
  • DIW deionized water
  • the glass substrate was ultrasonically treated using acetone and isopropyl alcohol (IPA) as solvents, and the glass substrate was treated with ultraviolet ray cleaning (UV Ozone) for 15 minutes.
  • IPA isopropyl alcohol
  • MXene solution (8 mg/mL in DI water) was applied to cover the surface of the glass substrate and waited for 3 minutes.
  • spin coating was performed at 2000 rpm for 60 seconds, and secondly, spin coating was performed at 6000 rpm for 90 seconds to evaporate the solvent of the MXene solution and form a MXene layer on the glass substrate.
  • the glass substrate on which the MXene layer was formed was heat-treated at a temperature of 150°C for 2 hours to increase the interlayer spacing of the MXene, thereby obtaining an electrode composed of a MXene layer-glass substrate.
  • the glass substrate coated with the MXene layer obtained in the above Reference Example 1 was heat-treated at 150° C. for 2 hours in a glove box under a nitrogen atmosphere. Then, a solution (2.5 mg/mL in isopropyl alcohol (IPA)) containing silver nanowires (AgNW) was applied onto the MXene layer, spin-coated at 2000 rpm for 60 seconds to position the silver nanowires on the MXene layer, and then heat-treated at 120° C. for 10 minutes in an air atmosphere to obtain an electrode composed of a conductive layer containing silver nanowires-MXene layer-glass substrate.
  • IPA isopropyl alcohol
  • a diluted MXene solution (0.5 mg/mL in DI water) containing the MXene of Preparation Example 1 was applied onto the conductive layer, and spin-coated at 2000 rpm for 60 seconds to form a MXene binder, thereby obtaining an electrode composed of conductive layer-MXene layer-glass substrate on which the MXene binder was formed.
  • a stretchable electrode was manufactured in the same manner as in Example 1, except that the glass substrate coated with the contact layer in Example 1 was not heat-treated, thereby not reducing the interlayer spacing of the maxene.
  • the glass substrate was sonicated using acetone and isopropyl alcohol (IPA) as solvents. Then, a solution containing silver nanowires (AgNWs) (2.5 mg/mL in isopropyl alcohol (IPA)) was applied onto the glass substrate, spin-coated twice at 2000 rpm for 60 s, and heat-treated at 150 °C for 10 min in an air atmosphere to promote interactions at the AgNW/AgNW interface.
  • IPA isopropyl alcohol
  • single-layer graphene was grown on copper (Cu) foil using chemical vapor deposition (CVD). Specifically, the copper foil was inserted into a quartz tube, heated to 1060°C using 15 sccm of H2, and annealed for 30 min. Then, CH4 gas, a graphene precursor, was supplied at 60 sccm for 30 min to grow graphene, and then rapidly cooled to room temperature to synthesize a single-layer graphene film on the copper foil.
  • CVD chemical vapor deposition
  • PMMA poly(methyl methacrylate)
  • Sigma-Aldrich solution 4.6 g/100 mL chlorobenzene solvent
  • the copper foil was then removed using ammonium persulfate ((NH 4 ) 2 S 2 O 8 ) etchant for 5 h, and the PMMA/graphene film was then floated on deionized water to wash away the residual etchant.
  • the graphene on the copper foil surface was rolled into a scroll shape due to surface tension, and then the PMMA/graphene film decorated with graphene scrolls was transferred to a cleaned glass substrate and rinsed with acetone for 1 h to remove the PMMA supporting layer, thereby obtaining an electrode composed of a graphene layer-glass substrate.
  • each image was taken using an atomic force microscope (NX-10, Park System).
  • Figure 10 is an atomic force microscope (AFM) image of a contact layer (Mxene) including MXene, silver nanowires (Mxene/AgNW) formed on the contact layer, and a MXene binder (Mxene/AgNW/binder) located at the interface of the MXene and silver nanowires, taken during the manufacturing process of Example 1.
  • AFM atomic force microscope
  • the maxene binder was located at the interface where the silver nanowires intersect each other and at the interface where the silver nanowires come into contact with the maxene layer.
  • FIG. 11 is a diagram showing Raman spectra for the electrodes and SEBS manufactured in Example 1 and Reference Example 1. Referring to FIG. 11, in the electrode manufactured in Example 1, a peak (Flake) corresponding to MXene, a peak (Tx) corresponding to the surface termination group of MXene, and a peak corresponding to SEBS were observed, confirming that the contact layer including MXene was well transferred without being separated from SEBS during the manufacturing process of Example 1.
  • FIG. 12 is a drawing showing XRD graphs for the electrodes manufactured in Example 1 and Reference Example 1.
  • the electrodes of Example 1 and Reference Example 1 in which heat treatment was performed on the MXene layer were measured to have interlayer spacings of MXene of 1.11 nm and 1.19 nm, which are less than 1.27 nm, which is the size of water molecules, and thus were confirmed to be suitable for a solution process.
  • the interlayer spacing of MXene measured for the electrode of Comparative Example 1 in which heat treatment was not performed on the contact layer including MXene was 1.33 nm, which is larger than 1.27 nm, and therefore deterioration due to interlayer insertion of water molecules was expected when used in a solution process.
  • Fig. 13 is a diagram showing O 1s XPS spectra for the electrodes manufactured in Example 1 and Reference Example 1.
  • Fig. 14 is a diagram showing FT-IR spectra for the electrodes of Example 1, Reference Example 1, and Comparative Example 2. Referring to Fig. 13, it can be confirmed that the intensity of the peak corresponding to Ti-OH indicating hydrogen bonding is stronger in the electrode of Example 1 than in the electrode of Reference Example 1.
  • FIG. 13 is a diagram showing O 1s XPS spectra for the electrodes manufactured in Example 1 and Reference Example 1.
  • Fig. 14 is a diagram showing FT-IR spectra for the electrodes of Example 1, Reference Example 1, and Comparative Example 2.
  • the hydration stability of the electrode was evaluated for the electrode of Example 1, in which the interlayer spacing of the MXene was measured to be 1.11 nm, and the electrode of Comparative Example 1, in which the interlayer spacing of the MXene was measured to be 1.33 nm.
  • FIG. 15 is a diagram showing the results of a hydration stability experiment on the electrodes manufactured in Example 1 and Comparative Example 1.
  • FIG. 16 is an AFM image of the contact layer including MXene for the electrodes manufactured in Example 1 and Comparative Example 1 after DI water coating. Referring to FIGS.
  • the electrode of Comparative Example 1 which did not perform heat treatment on the contact layer including MXene, showed significant performance degradation and damaged portions after DI water coating, whereas the electrode of Example 1, which performed heat treatment on the contact layer including MXene, showed no performance degradation or morphological change after DI water coating, confirming excellent moisture stability.
  • Example 1 For the electrodes of Example 1, Example 2, and Reference Examples 1 to 3, electrical conductivity and carrier mobility were measured.
  • the electrical contacts of the electrodes were shielded using copper tape to prevent the influence of the contact resistance of the spin-coated film.
  • the electrical conductivity of the electrodes was calculated by measuring the change in the slope of the current-voltage curve by scanning from -2 V to 2 V in 0.1 V increments using a Keithley 2400 source meter, and the carrier mobility was measured using Hall-effect analysis (HMS-5000, Ecopia Co. Ltd).
  • FIG. 17 is a diagram showing the electrical conductivity and carrier mobility of the electrodes of Example 1, Example 2, and Reference Examples 1 to 3.
  • the electrodes of Reference Examples 1 to 3 showed improved electrical conductivity but decreased carrier mobility when silver nanowires were applied on the MXene layer and when a MXene binder was additionally formed because the contact surface was the surface of the MXene layer where silver nanowires were positioned.
  • the electrodes of Examples 1 and 2 showed excellent electrical conductivity and carrier mobility at the same time because the silver nanowires existed between the MXene layer and the SEBS substrate layer and were not exposed at the contact surface. Furthermore, it was confirmed that the carrier mobility significantly increased in the electrode of Example 1 in which a MXene binder was further formed.
  • the optical transmittance at 550 nm and the sheet resistance were measured.
  • the optical transmittance was measured using UV-visible spectroscopy with a spectrophotometer (PerkinElmer, Lambda 465), and the sheet resistance (Rs) was determined using a four-point probe method connected to a Keithley 2400 source meter.
  • Fig. 18 is a diagram showing the light transmittance and sheet resistance (Rs) at 550 nm of the electrodes of Examples 1, 3, and 4. Referring to Fig. 18, it was confirmed that the electrodes of Examples 1, 3, and 4 all had excellent transparency, satisfying a light transmittance of 85% or more at 550 nm, and at the same time, had excellent conductivity, satisfying a sheet resistance of 30 ⁇ /sq or less.
  • the sheet resistance of the MXene layer and the graphene layer was measured using the same method as described above.
  • the sheet resistance of the MXene layer of Reference Example 1 was measured as 120 ⁇ /sq
  • the sheet resistance of the graphene layer of Comparative Example 3 was measured as 500 ⁇ /sq, confirming that the sheet resistance of the MXene layer was significantly lower than that of graphene.
  • the work functions of the electrodes of Examples 1, 3, 4, and 5 were measured using ultraviolet photoelectron spectroscopy (UPS).
  • UPS ultraviolet photoelectron spectroscopy
  • FIG. 19 is a diagram showing the work function of the electrodes of Examples 1, 3, 4, and 5.
  • the work function of the MXene-contacted stretchable electrode (MCSE) without surface modification was 4.73 eV
  • the work function of the MXene-contacted stretchable electrode surface-modified with PFSA (A-MCSE) was 5.71 eV
  • the work function of the MXene-contacted stretchable electrode surface-modified with PEI (MCSE/PEI) was 3.99 eV
  • the work function of the MXene-contacted stretchable electrode surface-modified with Crown-CPE (C-MCSE) was 3.79 eV. It was confirmed that the work function can be controlled to have a range of 3.70 eV to 5.71 eV depending on the surface modification material.
  • Example 1 A static stretching test and a cyclic stretching test were performed on the electrodes of Example 1, Example 2, and Comparative Example 2.
  • the electrodes were attached to a custom-fabricated stretching apparatus and the contacts were clamped to a rigid part of the stretching apparatus to maintain a consistent contact resistance.
  • Eutectic gallium indium (EGaIn) was applied over the contact area and supplemented with copper tape as contact pads.
  • the linear resistance between the copper contact pads was recorded using a Keithley 6500 digital multimeter.
  • the stretching apparatus stretched the electrode specimens with an initial length of 10 mm at a rate of 10 mm min until the tensile strain of the specimens reached 100%.
  • the electrode specimens were stretched 500 times from 0 to 40% tensile strain at 100 mm min -1 with real-time resistance measurements.
  • FIG. 20a is a diagram showing the results of a static elongation experiment on the electrodes of Example 1, Example 2, and Comparative Example 2.
  • FIG. 20b is a diagram showing the results of a cycling elongation experiment on the electrodes of Example 1 and Comparative Example 2.
  • Table 1 below shows the resistance change rate calculated by Equation 1 below according to the tensile strain for the electrodes of Example 1, Example 2, and Comparative Example 2.
  • Resistance change rate (%) [(RR 0 )/R 0 ] ⁇ 100 (The above R 0 is a resistance value measured for a stretchable electrode that has not undergone tensile deformation, and the above R is a resistance value measured for a stretchable electrode that has undergone tensile deformation.)
  • the electrode according to one embodiment of the present invention showed a smaller change in resistance as the tensile strain increased, compared to Comparative Example 2, which is a conventional electrode in which silver nanowires are impregnated in an elastomer substrate.
  • Comparative Example 2 which is a conventional electrode in which silver nanowires are impregnated in an elastomer substrate.
  • the resistance change according to the deformation due to stretching was significantly reduced in the electrode of Example 1 in which a MXene binder was formed.
  • FIG. 20b in a cycling stretching experiment, the process of stretching the electrode at a tensile strain of 40% and then recovering was repeated, and it was confirmed that the electrode according to the present invention showed a small change in resistance according to the number of cycles repeated.
  • FIG. 21 is an AFM image of the MXene layer of the stretchable electrode of Example 1 before stretching, at the time of stretching at an elongation of 40%, and after recovery.
  • an open crack occurs when the electrode specimen is stretched to a tensile strain of 40%, but the silver nanowires act as bridges across the crack, allowing electrical conductivity to be maintained.
  • MXene is a two-dimensional material, it suggests that even if a crack occurs during stretching, the conductive network formed by the silver nanowires can provide a conducting path for electricity to flow.
  • thermoplastic polyurethane (PU, Tecoflex SG-80A) was dissolved in a solvent having a volume-to-volume ratio of cyclohexanone and tetrahydrofuran (THF) of 10:1 to obtain a thermoplastic polyurethane solution of 2 mg/mL.
  • thermoplastic polyurethane solution After stirring the thermoplastic polyurethane solution for more than 1 hour in a glove box, 0.9 mg of (Ir(ppy) 2 acac) as a phosphorescent dopant, 5 mg of TCTA as a co-host, and 5 mg of TPBi were dissolved in 1 mL of the thermoplastic polyurethane solution in the same glove box to prepare a solution for forming a phosphorescent-based stretchable light-emitting layer.
  • a solution for forming a TADF-based stretchable light-emitting layer was prepared by dissolving 4CzIPN at a concentration of 1.5 mg/mL in the thermoplastic polyurethane solution obtained in the abovementioned Manufacturing Example 3.
  • a solution for forming a phosphorescent-based stretchable light-emitting layer was prepared in the same manner as in Manufacturing Example 3 above, except that a solution (180 mg/mL in toluene) containing SEBS (styrene-ethylene/butylene-styrene copolymer, Asahi Kasei TM H1062) elastomer was used instead of the thermoplastic polyurethane solution.
  • SEBS styrene-ethylene/butylene-styrene copolymer, Asahi Kasei TM H1062
  • the solutions for forming a stretchable light-emitting layer manufactured in Manufacturing Example 3 and Comparative Manufacturing Example 1 were spin-coated on an SEBS substrate at 2000 rpm for 60 seconds, respectively, and then the TADF-based stretchable light-emitting layer manufactured in Manufacturing Example 3 and the phosphorescence-based stretchable light-emitting layer manufactured in Comparative Manufacturing Example 1 were prepared as experimental specimens.
  • Magneto-PL and time-resolved photoluminescence (TRPL) analyses were performed on the stretchable light-emitting layers manufactured from the above Manufacturing Example 3 and Comparative Manufacturing Example 1. Magneto-PL and time-resolved photoluminescence analyses were performed on the stretchable light-emitting layer in a normal state and in a state where it was stretched to a strain ( ⁇ ) of 50%, respectively.
  • Magneto-PL recorded PL intensity as a function of magnetic field using a 405 nm laser as a light source, and TRPL spectra were obtained using a streak camera (Hamanatsu Photonics, Usho Optical Systems Co. Ltd.) and a 337 nm nitrogen pulsed laser.
  • Figure 22a is a diagram showing the results of Magneto-PL analysis of a TADF-based stretchable emitting layer (4CzIPN:PU) and a phosphorescent-based stretchable emitting layer (Ir(ppy) 2 acac:PU).
  • Figure 22b is a diagram showing the results of TRPL analysis of a TADF-based stretchable emitting layer (4CzIPN:PU) and a phosphorescent-based stretchable emitting layer (Ir(ppy) 2 acac:PU).
  • the emitting layer including 4CzIPN, a TADF molecule showed a PL peak red shift of approximately 12 nm under a tensile strain condition of 50%, indicating that a broader emission spectrum was caused by local aggregation of 4CzIPN molecules due to tensile strain.
  • the stretchable light-emitting layer based on phosphorescence according to one embodiment of the present invention maintained triplet collection efficiency due to strong SOC even under tensile strain conditions according to stretching, and the PL peak did not shift at all under tensile strain conditions of 50%.
  • the stretchable light-emitting layer based on phosphorescence has integrity when deformed, and thus is suitable for application to the stretchable organic light-emitting device to be implemented in the present invention.
  • a phosphorescence-based stretchable light-emitting layer was prepared as an experimental specimen in the same manner as in the comparative experiment of the TADF-based light-emitting layer and the phosphorescence-based stretchable light-emitting layer (1).
  • Fig. 23 is an atomic force microscope image of a stretchable light-emitting layer comprising thermoplastic polyurethane and SEBS elastomer as a matrix of the light-emitting layer.
  • thermoplastic polyurethane thermoplastic polyurethane
  • SEBS elastomer SEBS elastomer
  • the stretchable light-emitting layer forming solution manufactured in Manufacturing Example 3 was spin-coated at 2000 rpm for 60 seconds on a substrate containing SEBS elastomer, and a stretchable light-emitting layer was prepared as an experimental specimen.
  • the stretchable light-emitting layer was subjected to biaxial tensile strain and torsional strain on the experimental specimen, and images were taken, and optical microscope images were taken when the tensile strain ( ⁇ ) was 0%, 100%, and 200%.
  • FIG. 24 is a photograph taken when tensile strain and torsional strain are applied to a phosphorescent-based stretchable light-emitting layer deposited on a SEBS elastomer substrate, and an optical microscope image taken when the tensile strain ( ⁇ ) is 0%, 100%, and 200%.
  • ⁇ tensile strain
  • a mixture was obtained by adding 1 wt% of Triton-X 100 to poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS, Clevios TM P VP AI4083), and this mixture was mixed with perfluorosulfonic acid (PFSA) in a weight-to-weight ratio of 1:1.5 to prepare a solution for forming a stretchable hole injection layer.
  • PFSA perfluorosulfonic acid
  • the solution for forming a stretchable hole injection layer manufactured in Manufacturing Example 4 was spin-coated at 2000 rpm for 60 seconds on a cleanly washed glass substrate, and then the glass substrate was separated by immersing it in water, thereby preparing a stretchable hole injection layer manufactured in Manufacturing Example 4 as an experimental specimen.
  • X-ray photoelectron spectroscopy (XPS) analysis and ultraviolet photoelectron spectroscopy (UPS) spectrum analysis were performed on positions (P1, P2, P3, and P4, respectively) at the time points when Ar sputter etching was performed on the stretchable hole injection layer for 0 sec, 80 sec, 120 sec, and 200 sec.
  • the XPS analysis was performed by scanning using a monochromatic Al K ⁇ radiation source (1486.6 eV), and the UPS analysis was performed in the same manner as described in (3) Work function of the MXene-contacted stretchable electrode of Experimental Example 1.
  • FIG. 25a is a diagram showing the results of XPS analysis and UPS analysis according to the depth of the stretchable hole injection layer manufactured using the solution of Manufacturing Example 4.
  • FIG. 25b is a diagram showing the work function and F 1s atom content according to the depth of the stretchable hole injection layer manufactured using the solution of Manufacturing Example 4.
  • the content of fluorine atoms was high when the sputter etching time was 0 and 80 seconds, which indicates that PFSA, a perfluorinated compound, forms a self-assembled layer in which fluorine atoms are concentrated near the surface of the stretchable hole injection layer.
  • PFSA a perfluorinated compound
  • Example 7 Fabrication of a stretchable organic light-emitting device (ISOLED)
  • the solution for forming a stretchable hole injection layer manufactured in Manufacturing Example 4 was mixed on a roller for 1 hour before being used in device fabrication, and the solution for forming a stretchable light-emitting layer manufactured in Manufacturing Example 3 was prepared 12 hours before being used in device fabrication.
  • the solution for forming the stretchable hole injection layer was filtered through a 0.45 ⁇ m syringe PVDF filter, and then spin-coated at 4000 rpm for 60 seconds on the work function tuning layer of A-MCSE of Example 2. After that, a dense stretchable hole injection layer that is resistant to solvent attack of THF was formed through heat treatment at 100° C. for 30 minutes in an ambient air atmosphere. At this time, the thickness of the formed stretchable hole injection layer was approximately 82 nm.
  • the substrate was transferred to a glove box environment.
  • the solution for forming the stretchable light-emitting layer was filtered through a 0.2 ⁇ m syringe PVDF filter, and then spin-coated on the stretchable hole injection layer at 3000 rpm for 60 seconds. Thereafter, the stretchable light-emitting layer was formed by heat treatment at 90° C. for 5 minutes. At this time, the thickness of the formed stretchable light-emitting layer was approximately 50 nm.
  • the stretchable organic light-emitting device was encapsulated between two layers of SEBS films via drop casting in a glove box to protect the stretchable organic light-emitting device from oxygen and moisture.
  • Figure 26 is a diagram schematically showing the energy band of the stretchable organic light-emitting device manufactured in Example 7.
  • the current density, luminance, external quantum efficiency (EQE), and current efficiency of the light-emitting device were measured in a glove box filled with nitrogen gas.
  • the radiative characteristics were evaluated using an angle measurement setup in which a calibrated photodetector and a spectrometer were mounted on a rotating arm perpendicular to the apparatus.
  • Figure 27 is a diagram showing the current density, luminance, external quantum efficiency (EQE), and current efficiency of the stretchable organic light-emitting device manufactured in Example 7.
  • the maximum strain (%) refers to the tensile strain (%) at the point where the luminance of the light-emitting device decreases to 50% of the initial luminance.
  • the stretchable organic light-emitting device according to the present invention has higher current efficiency, external quantum efficiency, and maximum luminance compared to stretchable organic light-emitting devices of a conventionally reported method.
  • the tensile strain at the point where the luminance of the light-emitting device decreases to 50% of the initial luminance reaches 100%, and that it has excellent elasticity and excellent luminescence performance even in a stretched state.

Landscapes

  • Engineering & Computer Science (AREA)
  • Physics & Mathematics (AREA)
  • Manufacturing & Machinery (AREA)
  • Optics & Photonics (AREA)
  • Theoretical Computer Science (AREA)
  • General Engineering & Computer Science (AREA)
  • Human Computer Interaction (AREA)
  • General Physics & Mathematics (AREA)
  • Chemical & Material Sciences (AREA)
  • Dispersion Chemistry (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Electroluminescent Light Sources (AREA)

Abstract

La présente invention concerne une électrode étirable, une diode électroluminescente organique étirable la comprenant, et un procédé de fabrication de l'électrode étirable et de la diode électroluminescente organique étirable. Spécifiquement, la présente invention concerne une électrode étirable ayant un faible changement de résistance lors de l'étirement et une fonction de travail réglable, et une diode électroluminescente organique étirable qui comprend celle-ci et satisfait à la fois une élasticité et une efficacité lumineuse élevée.
PCT/KR2024/001917 2023-02-10 2024-02-08 Électrode étirable, diode électroluminescente organique étirable la comprenant, et son procédé de fabrication Ceased WO2024167347A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
KR20230017782 2023-02-10
KR10-2023-0017782 2023-02-10

Publications (1)

Publication Number Publication Date
WO2024167347A1 true WO2024167347A1 (fr) 2024-08-15

Family

ID=92263075

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/KR2024/001917 Ceased WO2024167347A1 (fr) 2023-02-10 2024-02-08 Électrode étirable, diode électroluminescente organique étirable la comprenant, et son procédé de fabrication

Country Status (2)

Country Link
KR (1) KR20240125852A (fr)
WO (1) WO2024167347A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN119423767A (zh) * 2025-01-08 2025-02-14 杭州祺福医疗科技有限公司 一种低阻抗电极贴片及其制备方法和应用

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR102866962B1 (ko) * 2025-03-19 2025-10-01 주식회사 신성씨앤티 맥신이 코팅된 그라파이트층을 포함하는 디스플레이 복합체

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20200124946A (ko) * 2019-04-25 2020-11-04 동우 화인켐 주식회사 전도성 고분자 조성물
KR20210086926A (ko) * 2019-12-31 2021-07-09 서울대학교산학협력단 이차원 전이 금속 카바이드 투명 전극을 포함하는 발광 소자 및 이의 제조 방법
US20210261415A1 (en) * 2020-02-20 2021-08-26 Korea Institute Of Science And Technology Transition metal carbonitride mxene films for emi shielding

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20200124946A (ko) * 2019-04-25 2020-11-04 동우 화인켐 주식회사 전도성 고분자 조성물
KR20210086926A (ko) * 2019-12-31 2021-07-09 서울대학교산학협력단 이차원 전이 금속 카바이드 투명 전극을 포함하는 발광 소자 및 이의 제조 방법
US20210261415A1 (en) * 2020-02-20 2021-08-26 Korea Institute Of Science And Technology Transition metal carbonitride mxene films for emi shielding

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
CHEN JIAXIN, LIU XINYA, LI ZIQING, CAO FA, LU XIANG, FANG XIAOSHENG: "Work‐Function‐Tunable MXenes Electrodes to Optimize p‐CsCu 2 I 3 /n‐Ca 2 Nb 3‐ x Ta x O 10 Junction Photodetectors for Image Sensing and Logic Electronics", ADVANCED FUNCTIONAL MATERIALS, WILEY - V C H VERLAG GMBH & CO. KGAA, DE, vol. 32, no. 24, 10 June 2022 (2022-06-10), DE , pages 2201066, XP093198369, ISSN: 1616-301X, DOI: 10.1002/adfm.202201066 *
WANG PENGCHANG, ZHANG CHI, WU MAJIAQI, ZHANG JIANHUA, LING XIAO, YANG LIANQIAO: "Scalable Solution-Processed Fabrication Approach for High-Performance Silver Nanowire/MXene Hybrid Transparent Conductive Films", NANOMATERIALS, MDPI, vol. 11, no. 6, 21 June 2021 (2021-06-21), pages 1360, XP093198368, ISSN: 2079-4991, DOI: 10.3390/nano11061360 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN119423767A (zh) * 2025-01-08 2025-02-14 杭州祺福医疗科技有限公司 一种低阻抗电极贴片及其制备方法和应用

Also Published As

Publication number Publication date
KR20240125852A (ko) 2024-08-20

Similar Documents

Publication Publication Date Title
WO2024167347A1 (fr) Électrode étirable, diode électroluminescente organique étirable la comprenant, et son procédé de fabrication
WO2020130592A1 (fr) Dispositif électroluminescent à base de pérovskite à halogénure métallique et son procédé de fabrication.
WO2013055138A2 (fr) Dispositif d'affichage électroluminescent organique simplifié et son procédé de fabrication
WO2010074432A1 (fr) Polymère conducteur, composition polymère, film et dispositif photoélectrique organique qui les comprenant
WO2014133373A1 (fr) Elément électronique employant une électrode hybride ayant une fonction de travail et une conductivité élevées
WO2016072810A1 (fr) Dispositif électroluminescent pérovskite contenant une couche tampon d'excitons et procédé pour sa fabrication
WO2018097666A2 (fr) Composé ionique, composition de revêtement et dispositif électroluminescent organique le comprenant
WO2011055933A9 (fr) Composition pour dispositif photoélectrique organique, dispositif photoélectrique organique l'utilisant et dispositif d'affichage intégrant ce dernier dispositif
WO2018021794A1 (fr) Procédé de préparation d'un film de composé de pérovskite hautement efficace et cellule solaire le comprenant
WO2020213814A1 (fr) Dispositif électroluminescent en pérovskite comprenant une couche de passivation et son procédé de fabrication
WO2016072809A1 (fr) Couche émettant de la lumière pour dispositif électroluminescent pérovskite, son procédé de fabrication et dispositif électroluminescent pérovskite l'utilisant
WO2016072807A1 (fr) Procédé de fabrication d'un corps électroluminescent à base de particules nanocristallines de pérovskite dont un ligand organique est substitué, corps électroluminescent à base de particules nanocristallines ainsi fabriqué, et dispositif électroluminescent l'utilisant
WO2022145775A1 (fr) Nouveau composé et dispositif électroluminescent organique le comprenant
WO2021025519A1 (fr) Élément photoélectrique pérovskite et son procédé de fabrication
WO2014133285A1 (fr) Film mince conducteur, son procédé de production et élément électronique le contenant
WO2022145774A1 (fr) Nouveau composé et dispositif électroluminescent organique le comprenant
WO2011081302A2 (fr) Polymère conducteur, composition de polymère conducteur, film de composition de polymère conducteur et dispositif photoélectrique l'utilisant
WO2016148382A1 (fr) Dispositif électroluminescent organique
WO2019146978A1 (fr) Polymère, composition de revêtement le comprenant, et dispositif électroluminescent organique l'utilisant
WO2015084090A1 (fr) Composition de couche de transport de trous comprenant un matériau de transport de trous polymère comprenant une double liaison réticulable et un agent de réticulation comprenant au moins deux groupes thiol et son utilisation
WO2021145639A1 (fr) Polymère et diode électroluminescente organique l'utilisant
WO2015037966A1 (fr) Copolymère et une cellule solaire organique le comprenant
WO2023043039A1 (fr) Nouveau composé pour dispositif électroluminescent, et dispositif électroluminescent organique le comprenant
WO2021107645A1 (fr) Élément photoélectrique à pérovskite et son procédé de fabrication
WO2024014798A1 (fr) Composite de transport de charge et procédé de formation de motif à haute résolution pour une couche de transport de charge le comprenant, ainsi que composition de couche de transport de charge et dispositif électroluminescent organique le comprenant

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 24753668

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE